[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

CN104755523A - Resin mixture based on vinyl ester urethane resin and use thereof - Google Patents

Resin mixture based on vinyl ester urethane resin and use thereof Download PDF

Info

Publication number
CN104755523A
CN104755523A CN201380055671.1A CN201380055671A CN104755523A CN 104755523 A CN104755523 A CN 104755523A CN 201380055671 A CN201380055671 A CN 201380055671A CN 104755523 A CN104755523 A CN 104755523A
Authority
CN
China
Prior art keywords
resin
methyl
compound
reaction
resin compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201380055671.1A
Other languages
Chinese (zh)
Inventor
M·莱特诺
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hilti AG
Original Assignee
Hilti AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hilti AG filed Critical Hilti AG
Publication of CN104755523A publication Critical patent/CN104755523A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/16—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/284—Compounds containing ester groups, e.g. oxyalkylated monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3218—Polyhydroxy compounds containing cyclic groups having at least one oxygen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/83—Chemically modified polymers
    • C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00715—Uses not provided for elsewhere in C04B2111/00 for fixing bolts or the like

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention relates to a resin mixture comprising a vinyl ester urethane resin as a base resin, in which the vinyl ester urethane resin can be obtained by (i) reacting a dianhydrohexitol-compound with a diisocyanate and subsequently (ii) reacting the obtained product with a hydroxy-substituted (meth)acrylate. The advantage of the base resin is that it can be obtained entirely from starting compounds based on renewable raw material. Said resin mixture is suitable, amongst other things, as a binding agent for reaction resin compositions, through which chemical fixing systems can be provided.

Description

Based on resin compound and the application thereof of vinyl ester urethane resins
Technical field
The present invention relates to the vinyl ester urethane resins had based on renewable raw materials, particularly based on the resin compound of resin based on the vinyl ester urethane resins of two dewatering hexitol, the reaction resin mortar containing this resin compound and its application fixed for chemistry.
Background technology
Know already based on the application of free-radical curable compound as the reaction resin mortar of binding agent.In technique for fixing field, realize resin compound as organic binder bond for chemical fastening techniques, such as, used as pin joint composition.Refer to joint composition herein, it is prepared as multicomponent system, and wherein a kind of component comprises resin compound, and another kind of component comprises solidified nature reagent.The composition of other routines, such as solvent comprises reactive solvents (reactive diluent) and can be included in described a kind of component and/or in described another kind of component.By mixing this two kinds of components, then being formed by free radical, cause curing reaction and polyreaction, and described resin solidification being thermosetting resin.Vinyl ester resin and unsaturated polyester resin is used as free-radical curable compound frequent (especially for chemical fastening techniques).
Due to the characteristic that it is favourable, vinyl ester resin (particularly vinyl ester urethane resins) is as base resin, and methacrylic ester such as the hydroxyalkyl methacrylate that its aromatic diisocyanate by monomer or polymer-type and hydroxyl replace obtains.Such as EP0713015 B1 describes and has unsaturated polyester resin, and vinyl ester resin comprises the pin joint composition of resin based on vinyl ester urethane resins.The compound of this system based on classical petroleum chemistry, its Raw from fossil feedstock source, as oil obtain.
As everyone knows, fossil feedstock source, as oil, is not inexhaustible, and by exhaustion at certain time.Situation about reducing for the availability in fossil feedstock source is dangerous, and perhaps the required compound of the high request namely proposed for chemical fixed system no longer can obtain.
Therefore, demand has the substituted systems based on renewable raw materials of the high-content carbon from renewable raw materials in the future, also can provide the chemical fixed system of highly-specialised further in the future.
Summary of the invention
Therefore the object of the invention is to, a kind of reaction resin mortar for chemical fastening techniques is provided, its resin Composition comprises base resin and optional other compositions (as reactive diluent), and it has the carbon from renewable raw materials of very high-content.
This object solves based on resin based on the vinyl ester urethane resins of two anhydrohexose alkylol cpd by using.Such advantage is, can trace back to starting compound to synthesize base resin, and it can be obtained with enough quality and quantities by renewable raw materials.
In order to understand the present invention better, the following explanation of term used herein is considered to be reasonably.Refer in the present invention:
-" base resin " is pure, solidified nature or curable compound, himself or adopt (not being included in base resin) such as reaction reagent such as solidified nature reagent, promotor to be solidified by polyreaction; Described curable compound can be monomer, dipolymer, oligopolymer and prepolymer;
-" resin concentrates " be synthesis after (not being separated base resin) base resin prepare product, it may comprise reactive diluent, stablizer and catalyzer (also referred to as resulting solution);
-" resin compound " refers to the mixture be made up of resin concentrates and promotor and stablizer and other optional reactive diluents; This term and term " organic binder bond " synonym use;
The mixture that-" reaction resin mortar " is made up of resin compound and inorganic additional material; Term " component A " synonym uses herein;
-" solidified nature reagent " is the material causing base resin to be polymerized (solidification);
The mixture that-" solidifying agent " is made up of solidified nature reagent and organic and/or inorganic additional material; Term " B component " synonym uses herein;
-" promotor " is the compound that can promote polyreaction (solidification), and it is for promoting the formation of radical initiator;
-" stopper " is the compound that can suppress polyreaction (solidification), its disposable (einmal) is for avoiding polyreaction and avoiding radical polymerizable compound in the less desirable polymerization of the too early generation of lay up period thus, wherein these compounds use with so a small amount of usually, and gel time is not affected; On the other hand, the polyreaction of stopper for occurring immediately after postponing to add solidified nature reagent, wherein these compounds use with such amount usually, namely make gel time influenced;
-" reactive diluent " is liquid or low viscous base resin, it dilutes other base resins, resin concentrates or resin compound, and viscosity required when providing it to apply thus, comprise the functional group can reacted with base resin, and become the composition through curing composition (mortar) when being polymerized (solidification) with major portion;
-" gel time " adopts unsaturated polyester resin or the Vinylite of peroxide cure usually for it, and the time of the cure stage of resin corresponds to gel time, and wherein the temperature of resin is increased to+35 DEG C by+25 DEG C.This roughly corresponds to such time period, and wherein the mobility of resin or viscosity are still in certain limit, and described reaction resin or reactive resin compositions still can easily be processed or process;
-" gelation time drift " is (for the special time period selected, such as 30 or 60 days), refer to this phenomenon, when the time point of solidification is different with the reference substance standard times point of solidification, such as after preparation feedback resin or reactive resin compositions 24 is constantly little, and viewed gel time departs from the time point of reference substance;
-" mortar material " refers to a kind of preparation, and it is except reactive resin compositions is also containing other organic and/or mineral filler, and it can former state be directly used in chemical fixing;
-" two-pack ash slurry system " refers to a kind of system, it comprises component A (reaction resin mortar) and B component (solidifying agent), two kinds of wherein said components are separately deposited with inhibited reaction, and the solidification of reaction resin mortar is only occurred after its mixing;
-" (methyl) vinylformic acid .../... (methyl) vinylformic acid ... " refer to " methacrylic acid .../... methacrylic acid ... " and " vinylformic acid .../... vinylformic acid .... "-compound all should be included;
-" vinyl ester urethane " refers to vinyl ester, and its secondary hydroxyl reacts with polyisocyanates in polyaddition, generates ammonia ester bridge thus;
-" renewable raw materials " refers to raw material, the particularly organic substance of plant or animal-origin, it is used for industry as raw material whole or in part, and its to be different from fossil feedstock be biorenewable, i.e. renewable in the time period of suitably (ü berschaubar); Comprise non-mineral or non-fossil feedstock, it may be used for industry or industry and commerce complete processing;
-" cold-curing " refers to that this resin compound and reaction resin mortar can at room temperature solidify completely.
Reaction resin mortar is prepared usually in the following way: optionally to add together with catalysts and solvents, particularly reactive diluent in reactor for the preparation of the starting compound needed for base resin and react to each other.When reaction terminates afterwards and optionally started to react, in order to package stability, stopper is added in reaction mixture, obtains so-called resin concentrates thus.In resin concentrates, often add promotor solidify for base resin, optionally other stoppers (it can be identical or different with the stopper for package stability), in order to regulate gel time, and optionally other solvents (particularly reactive diluent), obtain resin compound thus.In this resin compound, the inorganic and/or organic additional material of blending is for the various performance of adjustment, as rheology and the concentration of base resin, obtains reaction resin mortar thus.
Preferred resin compound correspondingly contains at least one base resin, at least one reactive diluent, at least one promotor, at least one stopper.Reaction resin mortar also comprises inorganic and/or organic additional material except comprising above-mentioned resin compound, wherein particularly preferably inorganic additional material, as described in more detail below those.
The present invention is based on following design: provide a kind of resin compound containing base resin, the starting compound that described base resin can be made up of biomass and thus can being prepared by renewable raw materials.Correspondingly, starting compound is selected according to its potential, can be obtained by renewable raw materials.
First theme of the present invention relates to the resin compound with resin based on vinyl ester urethane resins, wherein said vinyl ester urethane resins is by (i) two anhydrohexose alkylol cpd and di-isocyanate reaction, and (methyl) vinylformic acid of obtained product and hydroxyl being replaced of (i i) subsequently reacts and obtains.
Successfully realize astoundingly, based on the vinyl ester urethane resins based on two dewatering hexitol resin basis on reaction resin mortar is provided, it has acceptable connecting joint supporting capacity, and thus its suitable examples is as being used for chemical fastening techniques as organic binder bond.
According to the present invention, synthesize for vinyl ester urethane resins the vulcabond used usually used as starting compound to be obtained by dihydroxy compound and di-isocyanate reaction, make described product to have isocyanate group in molecular end and on molecular backbone chain, to have two carbamate groups.Aptly, every mole of dihydroxy compound uses at least two diisocyanate, and under making often kind of situation, an isocyanate group of described vulcabond and a hydroxyl reaction of dihydroxy compound form urethano group.But preferably vulcabond adds with excessive a little, oligomeric substantially to prevent.(methyl) acrylate reactions that described terminal isocyanate groups replaces with a hydroxyl in each case.
In order to starting compound can be obtained by renewable raw materials, dihydroxy compound is a kind of two anhydrohexose alkylol cpd according to the present invention.Two anhydrohexose alkylol cpd, the two anhydrohexose alkylol cpd of Isosorbide-5-Nitrae or rather: 3,6-is the by product of starch industry.They can such as be obtained by the dehydration of D-hexitol, and D-hexitol is by simply reducing hexose acquisition.Thus described two anhydrohexose alkylol cpds are the chiral product that can be obtained by biomass.According to the configuration of two hydroxyls, divide into three kinds of isomer (Isosorbide (structure A), isomannite (structure B) and different iditol (structure C)), it is by being carried out hydrogenation and follow-up two dehydration obtains by D-Glucose, D-MANNOSE or L-fructose.
Thus the two anhydrohexose alkylol cpds used as raw material can be Isosorbides, isomannite, or different iditol, or can be the mixtures of these pair of anhydrohexose alkylol cpd.Hereinafter thus term " two anhydrohexose alkylol cpd " is interpreted as separately any mixture of independently compound and various individually oriented compound.Because Isosorbide the most extensively distributes, therefore it is preferably used for and di-isocyanate reaction as starting compound.
Described two anhydrohexose alkylol cpd and its preparation method itself are known, and corresponding product can commercially be buied.
In order to vulcabond also can be obtained by renewable raw materials, aptly, vulcabond is aliphatic vulcabond, as tetramethylene diisocyanate, and hexamethylene diisocyanate or decamethylene vulcabond.
The advantage that the application of tetramethylene diisocyanate has is, it can by the C4-precursor structure unit of plant origin, namely succsinic acid obtains (Chemical Engineering & Technology Special Issue: material composition change, 31st volume, 5th phase, 647th page (2008), article " succsinic acid: the new chemical platform for the bio-based polymers from renewable resources ", I.Bechthold, K.Bretz, S Kabasci, R.Kopitzky and A.Springer).Author thinks that succsinic acid is one of basic chemical in the future, and it can be obtained by renewable raw materials.
In addition, also can obtain hexamethylene diisocyanate (HDMI) by renewable raw materials at present, because according to US Patent No. 8,421,879 corresponding precursors (hexanodioic acid) can obtain from biomass.
The advantage that the application of decamethylene vulcabond has equally is, it can be obtained by the C10-precursor structure unit (i.e. sebacic acid) of plant origin.The C10-precursor structure unit that can be obtained by bio-based Viscotrol C has a detailed description in the literature (European Journal of LipidScience and Technology, special issue: oil & fat is used for chemical industry as renewable resources, 112nd volume, 1st phase, 10th page (2010), article " Viscotrol C is used for chemical industry as renewable resources ", Hatice Mutlu and Michael A.R.Meier).Author also thinks at this, and Viscotrol C is the source of the very valuable renewable raw materials for chemical industry.
But in addition, other vulcabond that can be obtained by renewable raw materials also can be used according to the invention, such as, from lipid acid or other vulcabond of originating, as described in WO2011/098272 A2.
(methyl) acrylate that hydroxyl replaces also can be obtained by renewable raw materials.Particularly it relates to aliphatic series (methyl) acrylic acid hydroxy alkyl ester, and as (methyl) hydroxyethyl methacrylate or (methyl) hydroxyethyl acrylate, wherein methacrylate compound is particularly preferred.
(CEPmagazine.org can be obtained by glycerin obtained for the synthesis of the propylene glycol needed for Rocryl 410, the article of www.aiche.org/cep (in August, 2007), SuzanneShelley " obtains the renewable approach of propylene glycol ").Glycerine is the main by product of preparation biofuel.Therefore, for preparing propylene glycol, it is the cheapness of convenient source, and the substitute of sustainable and environmental protection, it can be obtained by oil.
Equally can by raw material as oxyethane and their derivative for the synthesis of the ethylene glycol needed for methacrylate, such as glycols (its can from biomass as molasses (Molasse) or sugarcane obtain) obtains.
Described methacrylic acid C 2-and C 3-hydroxy alkyl ester can commercially be buied.
, but (methyl) acrylate also having other hydroxyl that can be obtained by renewable raw materials to replace can be used according to the invention in addition.
Particularly preferred base resin has following formula:
Wherein n is 4,6 or 10, R is hydrogen or methyl.
If all starting compounds are obtained by renewable raw materials (as biomass), and in order to prepare resin compound, prepare by vinyl ester urethane resins form in hydroxypropyl methacrylate or methacrylate 65 % by weight solution, then the carbon content being up to 80% of resin compound can derive from renewable raw materials.
In a preferred embodiment in accordance with this invention, described resin compound contains other low viscosity, polymerizable compound, preferably can be obtained by renewable raw materials those, as reactive diluent, with where necessary, such as its viscosity of adapt when preparing vinyl ester urethane resins or its precursor.Described reactive diluent can in based on 90 to 10 % by weight of resin compound, and preferably 70 to 30 % by weight add.In this regard, see WO 09/156648 A1, WO 10/061097 A1, WO 10/079293 A1 and WO10/099201 A1, content is wherein incorporated into the application at this.
Described resin compound can be selected else containing any applicable reactive diluent.Aptly, described resin combination comprises aliphatic series or aromatics C 5-C 15(methyl) acrylate as reactive diluent, wherein particularly preferably (methyl) acrylate, it is selected from (methyl) hydroxyethyl methacrylate, 1，2-ethandiol two (methyl) acrylate, 1,3-PD two (methyl) acrylate, 1,2-butyleneglycol two (methyl) acrylate, BDO two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, (methyl) vinylformic acid styroyl ester, (methyl) vinylformic acid tetrahydro furfuryl ester, ethyl triglycol (methyl) acrylate, (methyl) vinylformic acid N, N-dimethyl aminoethyl ester, (methyl) vinylformic acid N, N-dimethylaminomethyl ester, (methyl) vinylformic acid acetoacetoxyethyl, (methyl) isobornyl acrylate, (methyl) 2-ethylhexyl acrylate, Diethylene Glycol two (methyl) acrylate, methoxy poly (ethylene glycol) list (methyl) acrylate, (methyl) acrylate trimethylcyclohexyl, (methyl) HEA, (methyl) vinylformic acid dicyclopentenyl oxygen ethyl ester and/or three cyclopentadienyl two (methyl) acrylate, dihydroxyphenyl propane-(methyl) acrylate, novolak epoxy two (methyl) acrylate, two-[(methyl) acryl-maleoyl] three ring-5.2.1.0. 2,6-decane, dicyclopentenyl oxygen ethyl crotonic acid esters, 3-(methyl) acryloyloxymethyl-three ring 5.2.1.0. 2,6-decane, 3-(methyl) cyclopentadienyl (methyl) acrylate, (methyl) isobornyl acrylate and naphthalane base (Decalyl)-2-(methyl) acrylate, PEG-bis-(methyl) acrylate, as PEG200 bis-(methyl) acrylate, TEG two (methyl) acrylate, (methyl) vinylformic acid solketal (Solketal) ester, (methyl) cyclohexyl acrylate, Phenoxyethyl two (methyl) acrylate, (methyl) methoxyethyl ethyl ester, (methyl) vinylformic acid tetrahydro furfuryl ester, (methyl) acrylate tert-buthyl and (methyl) vinylformic acid norcamphyl ester.In principle, other conventional polymerizable compound can also be used, separately or use with (methyl) crylic acid ester mixture, such as vinylbenzene, alpha-methyl styrene, alkylated styrenes, as t-butyl styrene, Vinylstyrene and allylic cpd, wherein said wherein can be obtained by the basic chemical based on renewable raw materials those be preferred.
Resist too early polyreaction (storage stability) in order to stabilization, and in order to regulate gel time and reactivity, described resin compound can comprise stopper.In order to ensure storage stability, described stopper is preferably in based on resin compound 0.0005 to 2 % by weight, and more preferably the amount of 0.01 to 1 % by weight exists.In order to regulate gel time and reactivity, described resin compound can additionally comprise 0.005 to 3 % by weight, preferably the stopper of 0.05 to 1 % by weight.
According to the present invention, usual the used stopper of the compound for free redical polymerization is suitable as described stopper, as well known to the skilled person those.
Too early polyreaction is resisted in order to stabilization; described resin compound and reaction resin mortar comprise stopper usually; as quinhydrones; the quinhydrones replaced; such as 4-methoxyphenol; thiodiphenylamine; benzoquinones or tert-butyl catechol (as such as described in EP1935860 A1 or EP 0965619A1); stable nitroxyl free radical; also referred to as N-oxygen base free radical; as piperidyl-N-oxygen base or Pyrrolidine-N-oxygen base, such as, described in DE 19531649 A1 those.Particularly preferably 4-hydroxyl-2,2,6,6-tetramethyl piperidine-N-oxygen base (hereinafter referred to as Tempol) is for stabilization, and its advantage had can also regulate gel time thus.
Preferably described stopper is selected from phenolic compound and non-phenolic compounds, as stable free radical and/or thiodiphenylamine.
As the phenolic inhibitor of component of reaction resin being often liberty of commerce base solidified nature, phenols can be considered, as 2-methoxyphenol, 4-methoxyphenol, 2,6 di tert butyl 4 methyl phenol, 2,4-DTBP, 2,6-, bis--tert.-butyl phenol, 2，4，6-trimethyl phenol, 2,4,6-tri-(dimethylaminomethyl) phenol, 4,4'-thiobis (3 methy 6 tert butyl phenol), 4,4'-isopropylidenediphenol, 6,6'-di-t-butyl-4,4'-two (2,6-, bis--tert.-butyl phenol), 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, 2,2'-methylene radical-two-p-cresol, pyrocatechol and butyl-catechol, as 4-tert-butyl catechol, 4,6-, bis--tert-butyl pyrocatechol, hydroquinones, as quinhydrones, 2-toluhydroquinone, TBHQ, 2,5 di tert butylhydroquinone, 2,6-di-tert-butyl hydroquinone, 2,6-dimethyl hydroquinone, TMHQ, benzoquinones, chloro-Isosorbide-5-Nitrae-the benzoquinones of 2,3,5,6-tetra-, methylbenzoquinone, 2,6-phlorone, naphthoquinones, or more two or more mixture in material.
Preferably phenothiazines is considered as non-phenolic inhibitor, as thiodiphenylamine and/or its derivative or their combination, or stable organic free radical, as jar (unit of capacitance) ten thousand oxygen base free radical and N-oxygen base free radical.
The stable N-oxygen base free radical (nitroxyl free radical) be applicable to can be selected from 1-oxygen base-2, 2, 6, 6-tetramethyl piperidine, 1-oxygen base-2, 2, 6, 6-tetramethyl piperidine-4-alcohol (also referred to as TEMPOL), 1-oxygen base-2, 2, 6, 6-tetramethyl piperidine-4-ketone (also referred to as TEMPON), 1-oxygen base-2, 2, 6, 6-tetramethyl--4-Carboxy-piperidin (also referred to as 4-carboxyl-TEMPO), 1-oxygen base-2, 2, 5, 5-tetramethylpyrrolidi-e, 1-oxygen base-2, 2, 5, 5-tetramethyl--3-carboxy pyrrole alkane (also referred to as 3-carboxyl-PROXYL), aluminium-N-nitrosophenylhydroxylamine, diethyl hydroxylamine, as described in DE 199 56 509.In addition the N-oxycompound be applicable to is that oximes is as ethylidenehydroxylamine, acetoxime, methyl ethyl ketone oxime, Whitfield's ointment oxime, benzo oxime, glyoxime, dimethyl glyoxime, acetone-O-(carbobenzoxy-(Cbz)) oxime etc.In addition, the ancymidol compound of oh group para-orientation or pyridine alkylol cpd passable, as not formerly described in disclosed patent application DE102011077248 B1, use as stablizer.
Depend on characteristic and the purposes of desired resin compound, described stopper can separately or as wherein two or more combinationally use.Being combined in this and can realizing synergy of phenols and non-phenolic inhibitor, and the adjustment of the display gel time of agonic adjustment reaction resin preparation substantially.
Preferably, the solidification of resinous principle adopts radical initiator (as superoxide) to cause.Except radical initiator, promotor can also be used.Obtain the reaction resin mortar of rapidly-curable thus, it is cold-curing, and namely it at room temperature solidifies.Usually promotor being be applicable to joined in resin compound well known to a person skilled in the art.These are such as amine, preferred tertiary amine and/or metal-salt.
The amine be applicable to is selected from following compound, such as, described in application US 2011071234 A1 those: dimethylamine, Trimethylamine 99, ethamine, diethylamine, triethylamine, Tri N-Propyl Amine, di-n-propylamine, Tri-n-Propylamine, Isopropylamine, Diisopropylamine, tri-isopropyl amine, n-Butyl Amine 99, isobutylamine, TERTIARY BUTYL AMINE, Di-n-Butyl Amine, diisobutylamine, tri-isobutylamine, amylamine, isobutylcarbylamine, di-iso-amylamine, hexylamine, octylame, lauryl amine, lauryl amine, stearylamine, monoethanolamine, diethanolamine, trolamine, amino-hexanol, oxyethyl group ethylamine, dimethyl-(2-chloroethyl) amine, 2 ethyl hexylamine, two (2-chloroethyl) amine, 2 ethyl hexylamine, two (2-ethylhexyl) amine, N-methyl stearylamine, dialkylamine, quadrol, N, N'-dimethyl-ethylenediamine, Tetramethyl Ethylene Diamine, diethylenetriamine, full methyl diethylenetriamine, Triethylenetetramine (TETA), tetren, 1，2-diaminopropane, dipropylenetriamine, tri propylidene tetramine, 1,4-Diaminobutane, 1，6-diaminohexane, 4-amino-1-diethylaminopentane, 2,5-diamino-2,5-dimethylhexane, trimethylhexamethylenediamine, N, N-dimethylaminoethanol, 2-(2-diethyl amino base oxethyl) ethanol, two (2-hydroxyethyl) oil base amine, three [2-(2-Hydroxy-ethoxy) ethyl] amine, 3-amino-1-propyl alcohol, methyl-(3-aminopropyl) ether, ethyl-(3-aminopropyl) ether, BDO-bis-(3-aminopropyl ether), 3-dimethylamino-1-propyl alcohol, 1-amino-2-propyl alcohol, 1-diethylamino-2-propyl alcohol, diisopropanolamine (DIPA), methyl-bis--(2-hydroxypropyl) amine, three-(2-hydroxypropyl) amine, 4-amino-2-butanols, 2-amino-2-methyl propyl alcohol, 2-amino-2-methyl propylene glycol, 2-amino-2-methylol propylene glycol, 5-diethyl (Aiethyl) amino-2 pentanone, 3-methyl aminopropionitrile, 6-aminocaprolc acid, 11-amino undecanoic acid, 6-aminocaprolc acid ethyl ester, 11-hexosamine isopropyl esters, hexahydroaniline, N-methylcyclohexylamine, N, N-dimethylcyclohexylamine, dicyclohexyl amine, N-ethyl cyclohexylamine, N-(2-hydroxyethyl) hexahydroaniline, two (2-hydroxyethyl) hexahydroaniline of N, N-, N-(3-aminopropyl)-hexahydroaniline, aminomethyl cyclohexane, hexahydrotoluene amine, six hydrogen benzylamines, aniline, methylphenylamine, DMA, N, N-Diethyl Aniline, N, N-dipropyl aniline, isobutyl-aniline, Tolylamine, diphenylamine, β-anilino-ethanol, two (hydroxyethyl) aniline, chloroaniline, amino-phenol, benzaminic acid and ester thereof, benzylamine, dibenzylamine, tribenzylamine, methyl dibenzylamine, α-phenylethylamine, xylidene(s), diisopropyl aniline, dodecyl polyaniline, amino naphthalenes, N-methylamino naphthalene, N, N-dimethylamino naphthalene, N, N-dibenzyl naphthalene, diamino-cyclohexane, 4,4'-diamino-dicyclohexyl methane, diamino dimethyidicyclohexyl-methane, phenylenediamine, benzene two methanediamine, benzidine, naphthylene diamine, Tolylamine, p-diaminodiphenyl, two (aminophenyl) propane of 2,2-, anisidine, aminothiophenol, ADP base ether, amino cresols, morpholine, N-methylmorpholine, N-phenyl-morpholine, hydroxyethyl morpholine, N-crassitude, tetramethyleneimine, piperidines, hydroxyethyl piperidine, pyrroles, pyridine, quinoline, indoles, pseudo-indole, carbazole, pyrazoles, imidazoles, thiazole, pyrimidine, quinoxaline, amino-morpholine, dimorpholine ethane, [2,2,2]-diazabicyclooctane and N, N-dimethyl-p-toluidine.
Preferred amine is anils and N; N-dialkyl arylamine; as N; accelerine, N; N-Diethyl Aniline, N; N-dimethyl-paratoluidine, N; N-two (hydroxyalkyl) arylamines, N; two (2-hydroxyethyl) aniline of N-, two (2-hydroxyethyl) Tolylamine of N, N-, N, N-two (2-hydroxypropyl) aniline, N; N-two (2-hydroxypropyl) Tolylamine, N; two (dimethylamino) ditan of two (3-methacryloyl-2-hydroxypropyl)-para-totuidine, N, N-dibutoxy hydroxypropyl-para-totuidine and 4, the 4'-of N-.
Polymer-type amine, as those by being obtained by the poly-addition of oxyethane on these amine by the polycondensation or pass through of two (hydroxyalkyl) aniline of N, N-and dicarboxylic acid, is also suitable as promotor.
The metal-salt be applicable to is, such as cobalt octoate or cobalt naphthenate, and carboxylic acid vanadium, carboxylic acid potassium, calcium carboxylates, copper carboxylate, manganese carboxylate or carboxylic acid zirconium.
If use promotor, then it is in based on described resin compound 0.01 to 10 % by weight, is preferably the amount use of 0.2 to 5 % by weight.
Another theme of the present invention is except above-mentioned resin combination, also containing organic binder bond, inorganic and/or organic additional material, and the reaction resin mortar of such as filler and/or other additive.
In reaction resin mortar, the ratio of resin compound is preferably based on 10 to 60 % by weight of described reaction resin mortar meter, and more preferably 20 to 30 % by weight.Therefore, the ratio of additional material is preferably based on 90 to 40 % by weight of described reaction resin mortar meter, is more preferably 80 to 70 % by weight.
Conventional filler can be used as filler, preferred mineral or class mineral filler, as quartz, glass, sand, quartz sand, silica powder, porcelain, corundum, pottery, talcum, silica (as fumed silica), silicate, clay, titanium dioxide, chalk, barite, feldspar, basalt, aluminium hydroxide, grouan or sandstone, polymer-type filler, as thermosetting resin, hydraulicity filler, as gypsum, unslaked lime or cement (such as high-alumina cement or portland cement), metal, such as aluminium, carbon black; In addition, timber, mineral or organic fiber etc., or two or more mixture in above-mentioned substance, it can be used as powder type, adds in granular form or with the form of formed body.Described filler can exist with arbitrary form, such as powder or powder or as formed body, such as with cylindrical, annular, spherical, flake, little bar-shaped, saddle type or crystalline form or other with fibers form (bat wool), and corresponding base particle preferably has the maximum diameter of 10mm.Filler is present in each composition, preferably with the amount being up to 90 % by weight, and particularly 3 to 85 % by weight, especially the amount of 5 to 70 % by weight exists.But what preferred and effect more obviously strengthened is spherical inert substance (spherical).
Other additive that can expect also has thixotropic agent, the such as optional fumed silica through organic aftertreatment, wilkinite, alkylcellulose and methylcellulose gum, castor oil derivative etc., softening agent is as phthalic acid ester or sebate, stablizer, static inhibitor, thickening material, toughner, curing catalysts, auxiliary rheological agents, wetting agent, color additive are as dyestuff or particularly pigment, such as fully mix to control it better for the difference of component is painted, or analogue, or two or more mixture in above-mentioned substance.Also have non-reacted thinner (solvent) passable, preferably with based on respective component (reaction resin mortar, solidifying agent) count the amount existence being up to 30 % by weight (such as 1 to 20 % by weight), as lower alkyl ketone such as acetone, two lower alkyl-lower alkane acid amides are as N,N-DIMETHYLACETAMIDE, low alkyl group benzene as dimethylbenzene or toluene, phthalic acid ester or paraffinic hydrocarbons, or water.
In a preferred embodiment of the invention, reaction resin mortar according to the present invention as two-pack or multicomponent system, particularly bicomponent system preparation, wherein said resinous principle and curing agent component separated with inhibited reaction.Therefore, the first component (component A) comprises reaction resin mortar, and second component (B component) comprises solidifying agent.Reach curable compound and solidified nature reagent thus be only just mixed with each other before being about to use and cause curing reaction.
Solidifying agent contains solidified nature reagent in order to cause the polymerization (solidification) of resinous principle.As mentioned above, this is radical initiator, preferred superoxide.
All superoxide for vinyl ester resin solidification well known by persons skilled in the art all can according to the present invention for solidifying the vinyl ester urethane resins based on two dewatering hexitol.This kind of superoxide comprises organic and inorganic peroxide, no matter is liquid or solid, wherein also can uses hydrogen peroxide.The example of the superoxide be applicable to is peroxycarbonates (formula-OC (O) OO-); peroxyester (formula-C (O) OO-); diacyl peroxide (formula-C (O) OOC (O)-), dialkyl peroxide (formula-OO-) etc.These can exist as oligopolymer or polymkeric substance.The example of the superoxide be applicable to of broad array is such as at application US2002/0091214-A1, and paragraph is described in [0018].
Preferably described superoxide is selected from organo-peroxide.The organo-peroxide be applicable to is: tertiary alkyl hydroperoxide, as tert-butyl hydroperoxide, with other hydroperoxide, as Cumene Hydroperoxide 80, peroxyester or peracid, as t-butyl peresters, benzoyl peroxide, peracetic acid ester and perbenzoate, lauroyl peroxide, comprise (two) peroxyester, cross ether as peroxide diethyl ether, cross ketone as methylethyl ketone peroxide.The organo-peroxide used as solidifying agent is often tertiary peresters or tertiary hydroperoxides, namely has the peralcohol of the tertiary carbon atom of Direct Bonding on-O-O-acyl group or-OOH group.But also can the mixture of these superoxide used according to the invention and other superoxide.Described superoxide also can be the superoxide of mixing, in a molecule, namely have the superoxide that two kinds of different superoxide carry unit.Preferred use benzoyl peroxide (BPO) is for solidification.
The solidifying agent of preferred two-pack ash slurry system also comprises inorganic additional material, and wherein said additional material is with can to add those in reaction resin mortar identical.
In the embodiment of a particularly preferred two-pack ash slurry system, component A except reaction resin mortar, also additionally comprise the hydraulicity or can the mineral compound of polycondensation, and B component also comprises water except solidified nature reagent.This kind of mortar material has a detailed description in DE 4231161 A1.Herein, preferred component A contain cement as the hydraulicity or can the mineral compound of polycondensation, such as portland cement or aluminate cement, wherein oxygen-freeization iron or cement containing suboxide iron be particularly preferred.Mineral compound as the hydraulicity can also use gypsum self or to use with the form of cement mixing.As can the mineral compound of polycondensation can also use silicates can polycondensation compound, particularly solubility, dissolved and/or containing the material of soft silica.
Described two-pack mortar system preference comprises component A and B component, they are separately placed in different containers with inhibited reaction, the device of such as multicell as the magazine (Kartusche) of the cylinder of multicell and/or multicell, from two kinds of components described in these containers by the effect of mechanical pressure or squeeze out under gaseous tension effect and mix.Another kind of possibility is, described two-pack ash slurry system is as the preparation of two-pack capsule, and it is inserted into boring and is loaded by the impact rotation of tightening member and destroy, and described two kinds of components of mortar material fully mix simultaneously.Preferred use cylinder system or injection system, wherein said two kinds of components extrude from the container separated, and are directed through static mixer, they are mixed equably wherein, are then exerted into boring by nozzle (preferably direct).
According to resin compound of the present invention, reaction resin mortar and two-pack ash slurry system can be mainly used in building field, such as, for concrete repair, as polymer concrete, as the coated material based on synthetic resins or as cold-curing pavement marker.It is particularly suitable for anchoring element, chemistry as crab-bolt, reinforcing bar, screw etc. is fixed, use in the borehole, in boring particularly in various substrate, particularly mineral substrate, as based on concrete, cellular concrete, brick material (Ziegelwerk), Dinas brickes, sandstone, lithotome etc. those.
The following examples are used for further illustrating the present invention.
Embodiment
Embodiment:
A) resin concentrates synthesis
A1) application of tetramethylene diisocyanate (TMDI)
Embodiment A 1.1
260g 1,3-PD dimethacrylate (Sarbio6200 is put in advance in the three-necked flask of 500mL; And 50gTMDI and by its blending 30mg tin dilaurate dioctyl tin (Tegokat216 Sartomer); Goldschmidt Industrial ChemicalCorporation), 20mg butylhydroxy toluene (BHT) and 40mg 4-hydroxyl-2,2,6,6-tetramethyl piperidine-N-oxygen base (Tempol).By the temperature adjustment process at 60 DEG C of this solution.Then 20g Isosorbide is lasted with 20 equal portions in the solution added for 60 minutes through stirring.After completing the adding of Isosorbide, mixture is heated to 70 DEG C, and stirs 5 hours at this temperature.By tlc, control the reaction of Isosorbide.After 5 hours, Isosorbide complete reaction.Subsequently by 50g Rocryl 410 (HPMA) (VISIOMER hPMA98; EvonikIndustries) last 60 minutes to be added dropwise to, and stir at 80 DEG C further until be less than 0.2% according to the NCO content of DIN EN 1242 mensuration.
Embodiment A 1.2
250g BDO dimethacrylate and 40g TMDI is added in advance in the three-necked flask of 500mL, and by its blending 60mg tin dilaurate dioctyl tin (Tegokat216), 40mg BHT and 90mg Tempol.By the temperature adjustment process at 60 DEG C of described solution.Then 20g Isosorbide is lasted with 20 equal portions in the solution added for 60 minutes through stirring.After completing the adding of Isosorbide, mixture is heated to 70 DEG C, and stirs 5 hours at this temperature.By tlc, control the reaction of Isosorbide.After 5 hours, Isosorbide complete reaction.Subsequently 40g HPMA is lasted 60 minutes to be added dropwise to, and stir until measure NCO content according to DIN EN 1242 to be less than 0.2% at 80 DEG C further.
A2) application of hexamethylene diisocyanate (HMDI)
Embodiment A 2.1
130g 1 is put in advance in the three-necked flask of 500mL, ammediol dimethacrylate (Sarbio6200), 130g 1,4-butyleneglycol dimethyl acrylate and 50g HMDI, and by its blending 30mg tin dilaurate dioctyl tin (Tegokat216), 20mg BHT and 40mg Tempol.Described solution is constant temperature process at 60 DEG C.Then 20g Isosorbide is lasted with 20 equal portions in the solution added for 60 minutes through stirring.After completing the adding of Isosorbide, mixture is heated to 70 DEG C, and stirs 5 hours at this temperature.By tlc, control the reaction of Isosorbide.After 5 hours, Isosorbide complete reaction.Subsequently 50g HPMA is lasted 60 minutes to be added dropwise to, and stir at 80 DEG C further until be less than 0.2% according to the NCO content of DIN EN 1242 mensuration.
Embodiment A 2.2
250g methacrylic acid (2 is put in advance in the three-necked flask of 500mL, 2-dimethyl-1,3-dioxolane-4-base) methyl esters (methacrylic acid solketal ester) and 45g HMDI, and by its blending 30mg tin dilaurate dioctyl tin (Tegokat216), 30mg BHT and 40mg Tempol.Described solution is constant temperature process at 60 DEG C.Then 20g Isosorbide is lasted with 20 equal portions in the solution added for 60 minutes through stirring.After completing the adding of Isosorbide, mixture is heated to 70 DEG C, and stirs 5 hours at this temperature.By tlc, control the reaction of Isosorbide.After 5 hours, Isosorbide complete reaction.Subsequently 45g HPMA is lasted 60 minutes to be added dropwise to, and stir at 80 DEG C further until be less than 0.2% according to the NCO content of DIN EN 1242 mensuration.
A3) application of decamethylene vulcabond (DMDI)
Embodiment A 3.1
230g 1 is put in advance in the three-necked flask of 500mL, ammediol dimethacrylate (Sarbio6200) and 60g DMDI, and by its blending 60mg tin dilaurate dioctyl tin (Tegokat216), 40mg BHT and 90mg Tempol.Described solution is temperature adjustment process at 60 DEG C.Then 20g Isosorbide is lasted with 20 equal portions in the solution added for 60 minutes through stirring.After completing the adding of Isosorbide, mixture is heated to 70 DEG C, and stirs 5 hours at this temperature.By tlc, control the reaction of Isosorbide.After 5 hours, Isosorbide reacts completely.In order to reduce the viscosity of mixture, dilute with 35g methacrylic acid tetrahydro furfuryl ester (Sarbio6100).Subsequently 40g HPMA is lasted 60 minutes to be added dropwise to, and stir at 80 DEG C further until be less than 0.2% according to the NCO content of DIN EN 1242 mensuration.
B) resin compound
B1) application of tetramethylene diisocyanate (TMDI)
Embodiment B 1.1
By the 380g resin concentrates prepared according to embodiment A 1.1 at 50 DEG C with 100g 1,4-butylene glycol dimethacrylate (BDDMA) and the 2g tertiary butyl-pyrocatechol (tBBK) blending, and at room temperature gel time is adjusted to 6 minutes by adding aromatic amine subsequently.
Embodiment B 1.2
By the 350g resin concentrates prepared according to embodiment A 1.2 at 50 DEG C with 90g BDDMA and 2g tBBK blending, and at room temperature gel time is adjusted to 6 minutes by adding aromatic amine subsequently.
B2) application of hexamethylene diisocyanate
Embodiment B 2.1
By the 380g resin concentrates prepared according to embodiment A 2.1 at 50 DEG C with 100g BDDMA and 2g tBBK blending, and at room temperature gel time is adjusted to 6 minutes by adding aromatic amine subsequently.
Embodiment B 2.2
By the 360g resin concentrates prepared according to embodiment A 2.2 at 50 DEG C with 90g BDDMA and 2g tBBK blending, and at room temperature gel time is adjusted to 6 minutes by adding aromatic amine subsequently.
B3) application of decamethylene vulcabond
Embodiment B 3.1
By the 300g resin concentrates prepared according to embodiment A 3.1 at 50 DEG C with 40g BDDMA and 2g tBBK blending, and at room temperature gel time is adjusted to 6 minutes by adding aromatic amine subsequently.
C) preparation feedback resin mortar
Mix mortar to prepare, will by B) there is the quartz sand of 30-45 weight part, the resin compound that the cement of 15-25 weight part and the fumed silica of 1-5 weight part are formed is mixed to form uniform mortar material in dissolver.
D) curing agent component
In order to prepare curing agent component, by 40g dibenzoyl peroxide, 250g water, 25g pyrogenic silica, the silica powder of 5g layered silicate and the suitable particle size distribution of 700g is mixed to form homogeneous compositions in dissolver.
Corresponding reaction resin mortar and curing agent component are mixed with each other with the volume ratio of 5:1 and measure its joint supporting capacity.
Measure inefficacy joint stress
In order to measure the inefficacy joint stress through curing composition, use anchorage screw M12, it is pinned in the boring in the concrete of diameter 14mm and the dark 72mm of boring with the reaction resin mortar material of embodiment.Relate to the boring of hammer drill cleaned very well herein, it solidifies all the time at 20 DEG C.Average failure load is determined by transfering to anchorage screw from center.Often kind of situation downside pin accesses 5 anchorage screws and measures its load value in solidification after 24 hours.Determined joint load σ (N/mm herein 2) be listed in the table below in 1 as mean value.
Market has the currently available products of very high joint load, such as the HITHY200A of Hilti company reaches about 30N/mm under comparable conditions 2value.This shows, the sample tested, and particularly based on the variant C1.2 of TMDI, has very promising part throttle characteristics.

Claims (16)

1. there is the resin compound of resin based on vinyl ester urethane resins, wherein said vinyl ester urethane resins is by (i) two anhydrohexose alkylol cpd and di-isocyanate reaction, and (methyl) acrylate reactions that obtained product and hydroxyl replace by (ii) subsequently obtains.
2. resin compound according to claim 1, wherein two anhydrohexose alkylol cpds of every mole at least with the di-isocyanate reaction of two moles.
3. according to the resin compound of claim 1 or 2, wherein (methyl) acrylate reactions of replacing of the product of reaction (i) of every mole and the hydroxyl of two moles.
4., according to the resin compound of aforementioned any one of claim, wherein said two anhydrohexose alkylol cpds are Isosorbides.
5., according to the resin compound of aforementioned any one of claim, wherein said vulcabond is aliphatic vulcabond.
6. resin compound according to claim 5, wherein said aliphatic vulcabond is tetramethylene diisocyanate, hexamethylene diisocyanate or decamethylene vulcabond.
7., according to the resin compound of aforementioned any one of claim, (methyl) acrylate that wherein said hydroxyl replaces is (methyl) acrylic acid hydroxy alkyl ester.
8. resin compound according to claim 7, wherein said (methyl) acrylic acid hydroxy alkyl ester is (methyl) hydroxyethyl methacrylate or (methyl) hydroxyethyl acrylate.
9., according to the resin compound of aforementioned any one of claim, the wherein said starting compound for the preparation of base resin can obtain from renewable raw materials.
10., according to the resin compound of aforementioned any one of claim, be wherein up to the carbon source of 80% in renewable raw materials.
11. reaction resin mortar, it comprises the resin compound any one of claim 1 to 10, and inorganic and/or organic additional material.
12. reaction resin mortar according to claim 11, wherein said additional material is selected from filler and additive.
13. according to the reaction resin mortar of claim 11 or 12, and wherein said resin compound exists with the amount of 10 to 60 % by weight.
14. dual component thermosetting resin ash slurry system, it comprises according to claim 11 to the reaction resin mortar any one of 13, and solidifying agent.
15. dual component thermosetting resin ash slurry system according to claim 14, wherein said solidifying agent comprises radical initiator as solidified nature reagent, and optional inorganic and/or organic additional material.
16. are used for the fixing purposes of chemistry according to claim 11 to the reaction resin mortar any one of 13.
CN201380055671.1A 2012-10-24 2013-10-22 Resin mixture based on vinyl ester urethane resin and use thereof Pending CN104755523A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102012219476.2 2012-10-24
DE102012219476.2A DE102012219476A1 (en) 2012-10-24 2012-10-24 Vinyl ester urethane resin-based resin composition and use thereof
PCT/EP2013/072018 WO2014064072A1 (en) 2012-10-24 2013-10-22 Resin mixture based on vinyl ester urethane resin and use thereof

Publications (1)

Publication Number Publication Date
CN104755523A true CN104755523A (en) 2015-07-01

Family

ID=49447566

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201380055671.1A Pending CN104755523A (en) 2012-10-24 2013-10-22 Resin mixture based on vinyl ester urethane resin and use thereof

Country Status (11)

Country Link
US (1) US9879111B2 (en)
EP (1) EP2912085B1 (en)
JP (1) JP6236087B2 (en)
CN (1) CN104755523A (en)
AU (1) AU2013336821A1 (en)
CA (1) CA2888875C (en)
DE (1) DE102012219476A1 (en)
DK (1) DK2912085T3 (en)
ES (1) ES2646914T3 (en)
RU (1) RU2650508C2 (en)
WO (1) WO2014064072A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105885004A (en) * 2016-06-22 2016-08-24 江南大学 Bio-based photo-curable polyurethane and photoresist prepared with same
CN110831996A (en) * 2017-07-03 2020-02-21 喜利得股份公司 Branched urethane methacrylate compound and use thereof
CN110831995A (en) * 2017-07-03 2020-02-21 喜利得股份公司 Reactive resin comprising urethane methacrylate compound, reactive resin component and reactive resin system and use thereof
CN112456938A (en) * 2020-12-10 2021-03-09 上海阳森精细化工有限公司 High-fluidity long-operation-period polyurethane urea cement concrete mortar terrace
CN113950498A (en) * 2019-06-18 2022-01-18 湛新比利时股份有限公司 Biobased polyurethane (meth) acrylates for coatings
TWI811584B (en) * 2020-11-06 2023-08-11 國家中山科學研究院 An accelerator for controlling the curing reaction time and temperature of vinyl ester resin and its preparation method

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012219477A1 (en) * 2012-10-24 2014-04-24 Hilti Aktiengesellschaft Process for the preparation of vinyl ester urethane resins based on dianhydrohexitol compounds and their use
US9663707B2 (en) * 2013-10-23 2017-05-30 Baker Hughes Incorporated Stimulation method using biodegradable zirconium crosslinker
CA2974933A1 (en) * 2015-02-19 2016-08-25 Showa Denko K.K. Low-temperature-curable cross-section repair material, and cross-section repairing method using the same
WO2016160135A1 (en) * 2015-04-03 2016-10-06 Henkel IP & Holding GmbH (meth)acrylate-functionalized extended isosorbide
DE102016117749A1 (en) 2015-10-22 2017-04-27 Fischerwerke Gmbh & Co. Kg Vinylesterurethanes such as urethane (meth) acrylates based on renewable raw materials containing synthetic resin attachment systems
CN109104865A (en) 2016-03-04 2018-12-28 陶氏环球技术有限责任公司 curable urethane acrylate composition
EP3489205A1 (en) 2017-11-28 2019-05-29 HILTI Aktiengesellschaft Isosorbide derivatives as reactive additives in reactive resins and chemical dowels
EP3489267A1 (en) 2017-11-28 2019-05-29 HILTI Aktiengesellschaft Biogenic oligomers as reactive supplements for curing of reactive resins
JP7104510B2 (en) * 2017-11-29 2022-07-21 クラレノリタケデンタル株式会社 Curable composition containing an alicyclic (meth) acrylic compound
EP3670612A1 (en) * 2018-12-18 2020-06-24 Hilti Aktiengesellschaft Use of urethane methacrylate compounds in reactive resin compositions
KR102449425B1 (en) * 2020-06-17 2022-10-04 주식회사 삼양사 Hydrophilic acryl-modified polyurethane and method for preparing the same, and waterborne coating composition prepared therefrom and method for preparing the same
DE102020213368A1 (en) 2020-10-22 2022-04-28 Tesa Se Proton sponges as a catalyst in adhesives and adhesives containing them
EP4357390A1 (en) 2022-10-18 2024-04-24 Hilti Aktiengesellschaft Biogenic methacrylates based on polycarbonate diols as reactive resins for curing reactive resins
EP4357313A1 (en) 2022-10-18 2024-04-24 Hilti Aktiengesellschaft Methacrylates formed from sugar derivatives as reactive components in reactive resins for chemical fixing

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4443563A (en) * 1983-06-08 1984-04-17 The Dow Chemical Company Polyurethanes based on 1;4-3:6 dianhydrohexitols
US5731366A (en) * 1994-10-28 1998-03-24 Dsm Resins B.V. Self-supporting plugging compound
CN101495530A (en) * 2006-07-28 2009-07-29 纳幕尔杜邦公司 Polytrimethylene ether-based polyurethane ionomers
CN101778879A (en) * 2007-07-03 2010-07-14 汉高公司 Acrylated urethanes, its preparation method and the curable compositions that comprises it
EP2433975A1 (en) * 2010-09-14 2012-03-28 Arkema Coatings Resins S.A.U. Improved powder coating compositions and a method for coating a substrate, such as a thermally sensitive substrate

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3111093A1 (en) * 1981-03-20 1982-10-07 Bayer Ag, 5090 Leverkusen METHOD FOR THE PRODUCTION OF CELL-SHAPED POLYURETHANE PLASTERS, IF ANY, USING DIANES OF THE DIANHYDRO-HEXITE SERIES
DE3940309A1 (en) * 1989-12-06 1991-06-13 Hilti Ag MOERTELMASSE
DE4231161A1 (en) 1992-09-17 1994-03-24 Hilti Ag Mortar and device for fixing anchoring means in boreholes
DE19531649A1 (en) 1995-08-29 1997-03-06 Basf Ag Dowel compound for chemical fastening technology
RU2233859C2 (en) * 1998-01-20 2004-08-10 Департамент экономики и промышленной политики Администрации Тверской области Gluing composition
DE19826412C2 (en) 1998-06-16 2002-10-10 Roehm Gmbh Odor-reduced, cold-curing (meth) acrylate reaction resin for floor coatings, floor coatings containing this reaction resin and process for producing such floor coatings
DE19956509A1 (en) 1999-11-24 2001-01-18 Basf Ag Inhibitor composition for (meth)acrylic acid stabilization comprises nitroxyl radical(s) (derivative) and a phenothiazine(s) and/or phenothiazine derivative(s)
EP1216991A1 (en) 2000-12-22 2002-06-26 Akzo Nobel N.V. Transportable and safely packaged organic peroxide formulations comprising reactive phlegmatizers
UA44468C2 (en) * 2001-04-04 2005-10-17 Ct Of Technologies Private Res A composition for the protection of buildings
CA2614050C (en) 2006-12-21 2015-04-21 Hilti Aktiengesellschaft Two-component reaction resin and method of fastening using the resin
US8040391B2 (en) 2007-08-06 2011-10-18 Panasonic Corporation White balance adjustment device, image capture device, white balance adjustment method, storage medium, and integrated circuit
US9120806B2 (en) * 2008-04-10 2015-09-01 Iowa Corn Promotion Board Dianhydrosugar production process
FR2931822B1 (en) 2008-05-30 2012-11-02 Arkema France BIOMASS - DERIVED METHYL METHACRYLATE, PROCESS FOR PRODUCING THE SAME, USES AND CORRESPONDING POLYMERS.
FR2938838B1 (en) 2008-11-27 2012-06-08 Arkema France PROCESS FOR THE PRODUCTION OF A METHYL METHACRYLATE DERIVED FROM BIOMASS
FR2940801B1 (en) 2009-01-06 2012-08-17 Arkema France PROCESS FOR THE PRODUCTION OF A METHYL METHACRYLATE DERIVED FROM BIOMASS
CA2753037A1 (en) 2009-02-24 2010-09-02 Gevo, Inc. Methods of preparing renewable butadiene and renewable isoprene
US20120156761A1 (en) 2009-07-02 2012-06-21 Verdezyne, Inc. Biological methods for preparing adipic acid
US9119774B2 (en) 2009-09-18 2015-09-01 Premier Dental Products Company Self-healing dental restorative formulations and related methods
JP5566701B2 (en) * 2010-01-12 2014-08-06 住友化学株式会社 Retardation film
EP2360196A1 (en) 2010-02-12 2011-08-24 Stichting Dutch Polymer Institute Polyurethane prepolymer and aqueous polyurethane dispersion
DE102011077248B3 (en) 2011-06-09 2012-09-27 Hilti Aktiengesellschaft Use of an inhibitor, resin mixture, reaction resin mortar, two - component mortar system and its use, and cartridge, cartridge or foil bag containing a two - component mortar system
EP2644589A1 (en) * 2012-03-30 2013-10-02 Cytec Surface Specialties, S.A. Radiation Curable (Meth)acrylated Compounds
US9484447B2 (en) 2012-06-29 2016-11-01 Intel Corporation Integration methods to fabricate internal spacers for nanowire devices

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4443563A (en) * 1983-06-08 1984-04-17 The Dow Chemical Company Polyurethanes based on 1;4-3:6 dianhydrohexitols
US5731366A (en) * 1994-10-28 1998-03-24 Dsm Resins B.V. Self-supporting plugging compound
CN101495530A (en) * 2006-07-28 2009-07-29 纳幕尔杜邦公司 Polytrimethylene ether-based polyurethane ionomers
CN101778879A (en) * 2007-07-03 2010-07-14 汉高公司 Acrylated urethanes, its preparation method and the curable compositions that comprises it
EP2433975A1 (en) * 2010-09-14 2012-03-28 Arkema Coatings Resins S.A.U. Improved powder coating compositions and a method for coating a substrate, such as a thermally sensitive substrate

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105885004A (en) * 2016-06-22 2016-08-24 江南大学 Bio-based photo-curable polyurethane and photoresist prepared with same
CN110831996A (en) * 2017-07-03 2020-02-21 喜利得股份公司 Branched urethane methacrylate compound and use thereof
CN110831995A (en) * 2017-07-03 2020-02-21 喜利得股份公司 Reactive resin comprising urethane methacrylate compound, reactive resin component and reactive resin system and use thereof
US11492328B2 (en) 2017-07-03 2022-11-08 Hilti Aktiengesellschaft Branched urethane methacrylate compounds and use thereof
CN110831995B (en) * 2017-07-03 2022-11-25 喜利得股份公司 Reactive resin comprising urethane methacrylate compound, reactive resin component and reactive resin system and use thereof
CN113950498A (en) * 2019-06-18 2022-01-18 湛新比利时股份有限公司 Biobased polyurethane (meth) acrylates for coatings
TWI811584B (en) * 2020-11-06 2023-08-11 國家中山科學研究院 An accelerator for controlling the curing reaction time and temperature of vinyl ester resin and its preparation method
CN112456938A (en) * 2020-12-10 2021-03-09 上海阳森精细化工有限公司 High-fluidity long-operation-period polyurethane urea cement concrete mortar terrace
CN112456938B (en) * 2020-12-10 2022-08-26 上海阳森精细化工有限公司 High-fluidity long-operation-period polyurethane urea cement concrete mortar terrace

Also Published As

Publication number Publication date
JP2015533905A (en) 2015-11-26
RU2650508C2 (en) 2018-04-16
ES2646914T3 (en) 2017-12-18
EP2912085A1 (en) 2015-09-02
CA2888875A1 (en) 2014-05-01
CA2888875C (en) 2021-02-16
AU2013336821A1 (en) 2015-05-14
JP6236087B2 (en) 2017-11-22
US9879111B2 (en) 2018-01-30
RU2015119366A (en) 2016-12-20
EP2912085B1 (en) 2017-08-09
DK2912085T3 (en) 2017-11-06
US20150232610A1 (en) 2015-08-20
WO2014064072A1 (en) 2014-05-01
DE102012219476A1 (en) 2014-04-24

Similar Documents

Publication Publication Date Title
CN104755523A (en) Resin mixture based on vinyl ester urethane resin and use thereof
CN104812720A (en) Reaction resin composition and use thereof
AU2014295033B2 (en) Resin mixture, reaction resin mortar, multi-component mortar system and use thereof
CN105102499B (en) Resin compound and its application based on epoxy (methyl) acrylate
CN105408278A (en) Reaction resin mortar, multi-component mortar system and use thereof
CN110831997B (en) Mixtures of radically curable compounds and their use
CA2889295A1 (en) Resin mixture based on vinyl ester resin, reactive resin mortar comprising the same and use thereof
AU2014289287A1 (en) Reaction resin composition and use thereof
US20240294677A1 (en) Method for fastening anchoring elements in boreholes
JP2022550704A (en) Storage-stable hardener composition for reactive resins
AU2018296606A1 (en) Urethane methacrylate compounds and use thereof
AU2018298307B2 (en) Reactive resins containing urethane methacrylate compounds, reactive resin components and reactive resin systems and use thereof
JP2022550516A (en) Storage-stable multi-component reactive resin system and its use

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20150701

RJ01 Rejection of invention patent application after publication